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Alkyl-carbonyl-iridium [Ir(CH3)(CO)(η2-O2CR′)(PPh3)2]+ (1, R′ = CH3, Ph, p-C6H4CH3) react with alkynes (RC CH; R = Ph, p-C6H4CH3) in the presence of NEt3 to give acyl-alkynyl-iridium Ir(C( O)CH3)(–C CR)(η2-O2CR′)(PPh3)2 (4) which further react with RC CH to give alkyl-carbonyl-cis-bis(alkynyl) iridium Ir(CH3)(CO)(C CR)2(PPh3)2 (5). cis-Bis(alkenyl)iridium complexes, Ir(–CH CH2)2(η2-O2CCH3)(PPh3)2 (6) and (η2-O2CCH3)(PPh3)2 (7) react with substituted alkynes RC CH (R = Ph, p-C6H4CH3, cyclohex-1-enyl) to give cis-bis(alkynyl) Ir(C CR)2(η2-O2CCH3)(PPh3)2 (9) that further react with RC CH to undergo the alkyne insertion reaction into the Ir–O bond to produce iridacycles containing vinyl acetate ligands, (–C CR)2(PPh3)2 (8). |
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